TWI815903B - Manufacturing method of adhesive sheet - Google Patents

Manufacturing method of adhesive sheet Download PDF

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Publication number
TWI815903B
TWI815903B TW108119835A TW108119835A TWI815903B TW I815903 B TWI815903 B TW I815903B TW 108119835 A TW108119835 A TW 108119835A TW 108119835 A TW108119835 A TW 108119835A TW I815903 B TWI815903 B TW I815903B
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Taiwan
Prior art keywords
adhesive layer
adhesive
plasma treatment
adhesive sheet
manufacturing
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TW108119835A
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Chinese (zh)
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TW202000827A (en
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彼谷美千子
山中大輔
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日商力森諾科股份有限公司
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Publication of TW202000827A publication Critical patent/TW202000827A/en
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Publication of TWI815903B publication Critical patent/TWI815903B/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/27—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
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    • H01L2224/48091—Arched
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    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
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    • H01—ELECTRIC ELEMENTS
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
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    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
    • H01L2224/922—Connecting different surfaces of the semiconductor or solid-state body with connectors of different types
    • H01L2224/9222—Sequential connecting processes
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    • H01L2224/92247—Sequential connecting processes the first connecting process involving a layer connector the second connecting process involving a wire connector
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    • H01—ELECTRIC ELEMENTS
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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    • H01L2924/181—Encapsulation

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Die Bonding (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)
  • Medicinal Preparation (AREA)

Abstract

本發明揭示一種黏著片的製造方法，包括：準備黏著片前驅物的步驟，所述黏著片前驅物具有基材及設置於基材上的黏著劑層；以及對黏著片前驅物中的黏著劑層的與基材相反一側的面實施電漿處理的步驟。 The invention discloses a method for manufacturing an adhesive sheet, which includes: preparing an adhesive sheet precursor, which has a base material and an adhesive layer disposed on the base material; and preparing the adhesive in the adhesive sheet precursor. The surface of the layer opposite to the substrate is subjected to a plasma treatment step.

Description

黏著片的製造方法 Manufacturing method of adhesive sheet

本發明是有關於一種黏著片的製造方法、切晶-黏晶一體型帶的製造方法、半導體裝置的製造方法、黏著劑的處理方法、被黏著體的固定方法及被黏著體的剝離方法。 The present invention relates to a manufacturing method of an adhesive sheet, a manufacturing method of a chip-bonding integrated belt, a manufacturing method of a semiconductor device, an adhesive processing method, a fixing method of an adherend, and a peeling method of an adherend.

黏著劑用於工業領域的各種用途中。於工業上，通常藉由調整交聯密度來控制黏著力(由交聯密度等引起的黏著劑自身的體(bulk)特性)。 Adhesives are used in various industrial applications. In industry, adhesion (bulk characteristics of the adhesive itself caused by cross-linking density, etc.) is usually controlled by adjusting the cross-linking density.

另一方面，已知有藉由對被黏著體實施表面處理來提高被黏著體與黏著劑的黏著性的方法。例如，於專利文獻1中記載有藉由對合成樹脂製品(被黏著體)實施電漿處理，從而合成樹脂製品與塗膜的黏著性提高。另外，於專利文獻2中記載有：於黏著片中，藉由對塑膠膜基材(被黏著體)實施電漿處理等而可提高塑膠膜基材表面對黏著劑層的錨固性。該些專利文獻中，就提高黏著性的觀點而言，均揭示有對被黏著體實施表面處理。 On the other hand, there is known a method of improving the adhesion between an adherend and an adhesive by subjecting the adherend to surface treatment. For example, Patent Document 1 describes that by subjecting a synthetic resin product (adherent) to plasma treatment, the adhesion between the synthetic resin product and a coating film is improved. In addition, Patent Document 2 describes that in an adhesive sheet, the anchorage of the surface of the plastic film base material to the adhesive layer can be improved by subjecting the plastic film base material (adherent) to plasma treatment or the like. In these patent documents, from the viewpoint of improving adhesion, it is disclosed that the adherend is subjected to surface treatment.

[現有技術文獻] [Prior art documents]

[專利文獻] [Patent Document]

專利文獻1：日本專利特開昭59-100143號公報 Patent document 1: Japanese Patent Application Publication No. Sho 59-100143

專利文獻2：日本專利特開2011-068718號公報 Patent Document 2: Japanese Patent Application Publication No. 2011-068718

但是，現有的黏著劑於黏著力的方面尚有改善的餘地。因此，本發明的主要目的在於提供一種黏著片的製造方法，其能夠製造具有黏著力優異的黏著劑層的黏著片。 However, existing adhesives still have room for improvement in terms of adhesion. Therefore, a main object of the present invention is to provide a method for manufacturing an adhesive sheet that can manufacture an adhesive sheet having an adhesive layer excellent in adhesive force.

作為被黏著體與黏著劑的黏著性的影響因素，除了黏著劑的黏著力(黏著劑自身的體特性)以外，亦有黏著劑相對於被黏著體的親和容易度(潤濕性)。但是，根據本發明者等人的研究而判明：於調整黏著劑的交聯密度來控制黏著劑的黏著力的方法中，黏著力與潤濕性存在所謂的權衡(trade off)的關係。例如，若以黏著力提高的方式調整交聯密度，則顯示出黏著劑對被黏著體的潤濕性下降的傾向。並且，基於該見解進一步研究的結果發現，藉由對黏著劑層實施電漿處理而非對被黏著體實施電漿處理，可降低被處理面的接觸角，提高黏著力，從而完成本發明。 As factors that influence the adhesion between the adherend and the adhesive, in addition to the adhesive force of the adhesive (the physical properties of the adhesive itself), there is also the ease of affinity (wetting) of the adhesive with respect to the adherend. However, studies by the present inventors have revealed that in the method of controlling the adhesive force of the adhesive by adjusting the cross-linking density of the adhesive, there is a so-called trade-off relationship between the adhesive force and the wettability. For example, if the cross-linking density is adjusted to increase the adhesive force, the wettability of the adhesive to the adherend tends to decrease. Further research based on this insight found that by applying plasma treatment to the adhesive layer instead of the adherend, the contact angle of the treated surface can be reduced and the adhesion can be improved, leading to the completion of the present invention.

本發明的一方面提供一種黏著片的製造方法，包括：準備黏著片前驅物的步驟，所述黏著片前驅物具有基材及設置於基材上的黏著劑層；以及對黏著片前驅物中的黏著劑層的與基材相反一側的面實施電漿處理的步驟。 One aspect of the present invention provides a method for manufacturing an adhesive sheet, which includes: preparing an adhesive sheet precursor, the adhesive sheet precursor having a base material and an adhesive layer disposed on the base material; and preparing the adhesive sheet precursor. The step of performing plasma treatment on the side of the adhesive layer opposite to the substrate.

電漿處理可為使用大氣壓電漿的電漿處理。電漿處理的處理溫度可低於基材的熔點或黏著劑層的熔點中任一較低者的溫度。 The plasma treatment may be plasma treatment using atmospheric pressure plasma. The treatment temperature of the plasma treatment may be lower than the melting point of the substrate or the melting point of the adhesive layer, whichever is lower.

黏著片的製造方法可進而包括於已實施電漿處理的黏著劑層的與基材相反一側的面上貼附保護材的步驟。保護材可為貼附於已實施電漿處理的黏著劑層一側的面藉由電漿處理進行了處理者。 The method of manufacturing an adhesive sheet may further include a step of attaching a protective material to the surface of the plasma-treated adhesive layer opposite to the base material. The protective material may be one in which the surface attached to the side of the adhesive layer that has been subjected to plasma treatment has been treated by plasma treatment.

於另一方面，本發明提供一種藉由所述製造方法而獲得的黏著片。 In another aspect, the present invention provides an adhesive sheet obtained by the manufacturing method.

於又一方面，本發明提供一種切晶-黏晶一體型帶的製造方法，包括：對於藉由所述製造方法而獲得的黏著片，於已實施電漿處理的黏著劑層的與基材相反一側的面上形成接著劑層的步驟。 In yet another aspect, the present invention provides a method for manufacturing a die-cutting-die-bonding integrated tape, which includes: for an adhesive sheet obtained by the manufacturing method, placing a plasma-treated adhesive layer between the adhesive sheet and the base material. The step of forming an adhesive layer on the opposite side.

於又一方面，本發明提供一種藉由所述製造方法而獲得的切晶-黏晶一體型帶。 In yet another aspect, the present invention provides a die-cutting-die-bonding integrated tape obtained by the manufacturing method.

於又一方面，本發明提供一種半導體裝置的製造方法，包括：將藉由所述製造方法而獲得的切晶-黏晶一體型帶的接著劑層貼附於半導體晶圓的步驟；將半導體晶圓、接著劑層及已實施電漿處理的黏著劑層單片化的步驟；自已實施電漿處理的所述黏著劑層拾取附著有接著劑層的半導體元件的步驟；以及經由接著劑層，將半導體元件接著於半導體元件搭載用支撐基板的步驟。 In another aspect, the present invention provides a method for manufacturing a semiconductor device, including the steps of attaching an adhesive layer of a die-cutting-die-bonding integrated tape obtained by the manufacturing method to a semiconductor wafer; The step of singulating the wafer, the adhesive layer and the adhesive layer that has been subjected to plasma treatment; the step of picking up the semiconductor element attached with the adhesive layer from the adhesive layer that has been subjected to plasma treatment; and via the adhesive layer , the step of bonding the semiconductor element to the supporting substrate for mounting the semiconductor element.

於又一方面，本發明提供一種黏著劑的處理方法，包括：對黏著劑實施電漿處理的步驟。電漿處理可為使用大氣壓電漿的電漿處理。電漿處理的處理溫度可低於黏著劑的熔點。 In another aspect, the present invention provides a method for treating an adhesive, including the step of subjecting the adhesive to plasma treatment. The plasma treatment may be plasma treatment using atmospheric pressure plasma. Plasma treatment can be performed at temperatures below the melting point of the adhesive.

於又一方面，本發明提供一種被黏著體的固定方法，包 括：經由藉由所述方法進行了處理的黏著劑，將第二被黏著體貼附於第一被黏著體的步驟。另外，於又一方面，本發明提供一種被黏著體的剝離方法，包括：利用水來對藉由所述方法進行了固定的被黏著體的第一被黏著體與黏著劑的界面或第二被黏著體與黏著劑的界面的至少一者進行處理，將第一被黏著體及第二被黏著體剝離的步驟。 In yet another aspect, the present invention provides a method for fixing an adherend, including It includes: a step of attaching the second adherend to the first adherend using the adhesive treated by the above method. In addition, in another aspect, the present invention provides a method for peeling off an adherend, including using water to remove the interface between the first adherend and the adhesive or the second interface of the adherend fixed by the method. A step of processing at least one of the interfaces between the adherend and the adhesive to peel off the first adherend and the second adherend.

根據本發明，可提供一種黏著片的製造方法，其能夠製造具有黏著力優異的黏著劑層的黏著片。另外，根據本發明，可提供一種使用藉由此種製造方法而獲得的黏著片的切晶-黏晶一體型帶的製造方法。另外，根據本發明，可提供一種使用藉由此種製造方法而獲得的切晶-黏晶一體型帶的半導體裝置製造方法。進而，根據本發明，可提供一種黏著劑的處理方法、被黏著體的固定方法及被黏著體的剝離方法。 According to the present invention, a method for manufacturing an adhesive sheet capable of manufacturing an adhesive sheet having an adhesive layer excellent in adhesive force can be provided. Furthermore, according to the present invention, it is possible to provide a method for manufacturing a die-cutting-die-bonding integrated belt using an adhesive sheet obtained by such a manufacturing method. In addition, according to the present invention, it is possible to provide a semiconductor device manufacturing method using a die-cutting-die-bonding integrated tape obtained by such a manufacturing method. Furthermore, according to the present invention, it is possible to provide a method for processing an adhesive, a method for fixing an adherend, and a method for peeling off an adherend.

10:基材 10:Substrate

20、20Aa:黏著劑層 20, 20Aa: Adhesive layer

20A:電漿處理後的黏著劑層 20A: Adhesive layer after plasma treatment

30、50:保護材 30, 50: protective material

40、40a:接著劑層 40, 40a: Adhesive layer

60:帶接著劑層的半導體元件 60: Semiconductor components with adhesive layer

70:打線接合線 70: Wire bonding wire

72:頂針 72:Thimble

74:抽吸夾頭 74:Suction chuck

80:半導體元件搭載用支撐基板 80:Support substrate for mounting semiconductor components

80a:表面 80a: Surface

92:樹脂密封材 92: Resin sealing material

94:焊球 94: Solder ball

100:黏著片前驅物 100:Adhesive sheet precursor

110:黏著片 110: Adhesive sheet

120:帶保護材的黏著片 120: Adhesive sheet with protective material

130:切晶-黏晶一體型帶 130: Crystal cutting-crystal bonding integrated belt

140:帶保護材的切晶-黏晶一體型帶 140: Crystal cutting-crystal bonding integrated belt with protective material

200:半導體裝置 200:Semiconductor devices

A:電漿處理 A: Plasma treatment

W:半導體晶圓 W: semiconductor wafer

Wa:半導體元件 Wa: semiconductor element

Ws:主面 Ws: Main side

圖1(a)~圖1(d)是示意性表示黏著片的製造方法的一實施形態的剖面圖。圖1(a)、圖1(b)、圖1(c)及圖1(d)是示意性表示各步驟的剖面圖。 1(a) to 1(d) are cross-sectional views schematically showing an embodiment of a method of manufacturing an adhesive sheet. 1(a), 1(b), 1(c) and 1(d) are cross-sectional views schematically showing each step.

圖2(a)~圖2(c)是示意性地表示切晶-黏晶一體型帶的製造方法的一實施形態的剖面圖。圖2(a)、圖2(b)及圖2(c)是示意性表示各步驟的剖面圖。 2(a) to 2(c) are cross-sectional views schematically showing an embodiment of a method for manufacturing a die-cutting-die-bonding integrated belt. 2(a), 2(b) and 2(c) are cross-sectional views schematically showing each step.

圖3(a)~圖3(f)是示意性表示半導體裝置的製造方法的一實施形態的剖面圖。圖3(a)、圖3(b)、圖3(c)、圖3(d)、圖3(e)及圖3(f)是示意性表示各步驟的剖面圖。 3(a) to 3(f) are cross-sectional views schematically showing an embodiment of a method of manufacturing a semiconductor device. 3(a), 3(b), 3(c), 3(d), 3(e) and 3(f) are cross-sectional views schematically showing each step.

圖4是示意性表示半導體裝置的一實施形態的剖面圖。 4 is a cross-sectional view schematically showing an embodiment of a semiconductor device.

以下，適宜參照圖式來對本發明的實施形態進行說明。但本發明並不限定於以下實施形態。以下實施形態中，除特別明示的情況以外，其構成要素(亦包含步驟等)並非必需。各圖中的構成要素的大小為概念性的大小，構成要素間的大小的相對關係並不限定於各圖所示的關係。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments. In the following embodiments, components (including steps, etc.) are not essential unless otherwise stated. The sizes of the constituent elements in each drawing are conceptual sizes, and the relative size relationship between the constituent elements is not limited to the relationship shown in each drawing.

本說明書中的數值及其範圍亦同樣如此，並非限制本發明者。本說明書中，使用「~」來表示的數值範圍表示包含「~」的前後所記載的數值分別作為最小值及最大值的範圍。於本說明書中階段性地記載的數值範圍內，一數值範圍所記載的上限值或下限值亦可替換成另一階段記載的數值範圍的上限值或下限值。另外，於本說明書中所記載的數值範圍內，該數值範圍的上限值或下限值可替換成實施例中所示的值。 The numerical values and their ranges in this specification are also the same and do not limit the inventor. In this manual, the numerical range represented by "~" means the range including the numerical values written before and after "~" as the minimum value and the maximum value respectively. Within the numerical ranges described in stages in this specification, the upper limit or lower limit described in one numerical range may also be replaced by the upper limit or lower limit of the numerical range described in another stage. In addition, within the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the Example.

於本說明書中，(甲基)丙烯酸酯是指丙烯酸酯或與其對應的甲基丙烯酸酯。 In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate.

[黏著片的製造方法] [Manufacturing method of adhesive sheet]

圖1(a)~圖1(d)是示意性表示黏著片的製造方法的一實施形態的剖面圖。本實施形態的黏著片的製造方法包括：準備具 有基材及設置於基材上的黏著劑層的黏著片前驅物的步驟(黏著片前驅物的準備步驟)；以及對黏著片前驅物中的黏著劑層的與基材相反一側的面實施電漿處理的步驟(電漿處理的實施步驟)。本實施形態的黏著片的製造方法可進而包括於已實施電漿處理的黏著劑層的與基材相反一側的面上貼附保護材的步驟(保護材的配置步驟)。 1(a) to 1(d) are cross-sectional views schematically showing an embodiment of a method of manufacturing an adhesive sheet. The manufacturing method of the adhesive sheet of this embodiment includes: preparation tool The steps of an adhesive sheet precursor including a base material and an adhesive layer disposed on the base material (preparation steps of the adhesive sheet precursor); and the step of preparing the adhesive sheet precursor on the side opposite to the base material of the adhesive layer. The step of implementing plasma treatment (implementation step of plasma treatment). The manufacturing method of the adhesive sheet of this embodiment may further include the step of attaching a protective material to the surface of the plasma-treated adhesive layer opposite to the base material (protective material placement step).

<黏著片前驅物的準備步驟> <Preparation steps for adhesive sheet precursor>

於本步驟中，準備作為電漿處理的對象的黏著片前驅物100(參照圖1(a))。黏著片前驅物100具有基材10、及設置於基材10上的黏著劑層20。 In this step, an adhesive sheet precursor 100 to be subjected to plasma treatment is prepared (see FIG. 1(a) ). The adhesive sheet precursor 100 has a base material 10 and an adhesive layer 20 provided on the base material 10 .

基材10只要為具有較藉由電漿處理而產生的熱更高的熔點(或者分解點或軟化點)者，則並無特別限制，可使用在黏著劑的領域中所使用的基材膜。基材膜較佳為於黏晶步驟中能夠擴張(expand)。作為此種基材膜，例如可列舉：聚對苯二甲酸乙二酯膜等聚酯系膜；聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚乙酸乙烯酯膜等聚烯烴系膜；聚氯乙烯膜、聚醯亞胺膜等塑膠膜等。基材10可對供形成黏著劑層20的面實施電暈處理等表面處理。 The base material 10 is not particularly limited as long as it has a higher melting point (or decomposition point or softening point) than the heat generated by plasma treatment, and a base film used in the field of adhesives can be used. . The base film is preferably capable of expanding during the die bonding step. Examples of such base films include polyester films such as polyethylene terephthalate films; polytetrafluoroethylene films, polyethylene films, polypropylene films, polymethylpentene films, and polyvinyl acetate films. Polyolefin films such as ester films; plastic films such as polyvinyl chloride films and polyimide films. The base material 10 may be subjected to surface treatment such as corona treatment on the surface on which the adhesive layer 20 is formed.

黏著劑層20是包含黏著劑成分的層。構成黏著劑層20的黏著劑成分只要為具有較藉由電漿處理而產生的熱更高的熔點(或者分解點或軟化點)者，則並無特別限制，較佳為於室溫(25℃)下具有黏著力，且對積層於黏著劑層20上的層(例如後述的 接著劑層)具有密接力者。構成黏著劑層20的黏著劑成分亦可含有基體樹脂(base resin)。作為基體樹脂，例如可列舉丙烯酸系樹脂、合成橡膠、天然橡膠、聚醯亞胺樹脂等。就減少黏著劑成分的殘膠的觀點而言，基體樹脂較佳為具有可與後述的交聯劑等反應的羥基、羧基等官能基。基體樹脂可為藉由紫外線、放射線等高能量射線而硬化的樹脂或者藉由熱而硬化的樹脂。基體樹脂較佳為藉由高能量射線而硬化者，更佳為藉由紫外線而硬化者(紫外線硬化型基體樹脂)。 The adhesive layer 20 is a layer containing an adhesive component. The adhesive component constituting the adhesive layer 20 is not particularly limited as long as it has a higher melting point (or decomposition point or softening point) than the heat generated by plasma treatment, and is preferably at room temperature (25 ℃), and has adhesive force to the layer laminated on the adhesive layer 20 (such as the later-described Adhesive layer) has strong adhesion. The adhesive component constituting the adhesive layer 20 may also contain a base resin. Examples of the base resin include acrylic resin, synthetic rubber, natural rubber, polyimide resin, and the like. From the viewpoint of reducing the adhesive residue of the adhesive component, the base resin preferably has functional groups such as hydroxyl group and carboxyl group that can react with a cross-linking agent to be described later. The base resin may be a resin hardened by high-energy rays such as ultraviolet rays or radiation, or a resin hardened by heat. The base resin is preferably hardened by high-energy rays, and more preferably hardened by ultraviolet rays (ultraviolet curable base resin).

於使用藉由高能量射線而硬化的樹脂作為基體樹脂的情況下，亦可視需要而併用光聚合起始劑。光聚合起始劑例如可列舉：芳香族酮化合物、安息香醚化合物、苯偶醯化合物、酯化合物、吖啶化合物、2,4,5-三芳基咪唑二聚物等。 When using a resin hardened by high-energy rays as the base resin, a photopolymerization initiator may be used together as necessary. Examples of the photopolymerization initiator include aromatic ketone compounds, benzoin ether compounds, benzil compounds, ester compounds, acridine compounds, 2,4,5-triarylimidazole dimers, and the like.

為了調整黏著力，黏著劑成分亦可含有能夠與基體樹脂的官能基形成交聯結構的交聯劑。交聯劑較佳為具有選自由環氧基、異氰酸酯基、氮丙啶基及三嗪基所組成的群組中的至少一種官能基。交聯劑可單獨使用一種，亦可組合使用兩種以上。 In order to adjust the adhesive force, the adhesive component may also contain a cross-linking agent that can form a cross-linked structure with the functional groups of the matrix resin. The cross-linking agent preferably has at least one functional group selected from the group consisting of an epoxy group, an isocyanate group, an aziridinyl group and a triazine group. One type of cross-linking agent may be used alone, or two or more types may be used in combination.

為了維持由電漿處理所帶來的效果，有效的是調整交聯劑的含量。相對於基體樹脂100質量份，交聯劑的含量較佳為5質量份以上，更佳為7質量份以上，進而佳為10質量份以上。若相對於基體樹脂100質量份而交聯劑的含量為5質量份以上，則有可抑制由電漿處理所帶來的效果衰減的傾向。相對於基體樹脂100質量份，交聯劑的含量可為30質量份以下。若相對於基體樹 脂100質量份而交聯劑的含量為30質量份以下，則有容易維持由電漿處理所帶來的效果的傾向，且有可抑制黏著劑層與保護材的密接性下降的傾向。 In order to maintain the effect brought about by the plasma treatment, it is effective to adjust the content of the cross-linking agent. The content of the cross-linking agent is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and still more preferably 10 parts by mass or more relative to 100 parts by mass of the base resin. If the content of the crosslinking agent is 5 parts by mass or more relative to 100 parts by mass of the base resin, the attenuation of the effect caused by the plasma treatment tends to be suppressed. The content of the crosslinking agent may be 30 parts by mass or less relative to 100 parts by mass of the matrix resin. If relative to the base tree When the content of the cross-linking agent is 30 parts by mass or less per 100 parts by mass of the grease, the effect of the plasma treatment tends to be easily maintained, and the decrease in the adhesion between the adhesive layer and the protective material tends to be suppressed.

黏著劑成分亦可含有其他成分。作為其他成分，例如可列舉：以促進基體樹脂與光聚合起始劑的交聯反應為目的而添加的胺、錫等觸媒；以適當地調整黏著特性為目的而添加的松香系、萜烯樹脂系等增黏劑(tackifier)；各種界面活性劑等。 The adhesive component may also contain other components. Examples of other components include: catalysts such as amines and tin added for the purpose of accelerating the cross-linking reaction between the base resin and the photopolymerization initiator; and rosins and terpenes added for the purpose of appropriately adjusting the adhesive properties. Tackifiers such as resin systems; various surfactants, etc.

於一實施形態中，黏著劑層20可為包含如下黏著劑成分的層，所述黏著劑成分含有具有羥基的丙烯酸系樹脂及具有異氰酸酯基的交聯劑。 In one embodiment, the adhesive layer 20 may be a layer including an adhesive component containing an acrylic resin having a hydroxyl group and a cross-linking agent having an isocyanate group.

作為基體樹脂的具有羥基的丙烯酸系樹脂，可藉由使包含具有羥基的(甲基)丙烯酸酯的單體成分聚合而獲得。聚合方法可自各種自由基聚合等公知的聚合方法中適宜選擇，例如可為懸浮聚合法、溶液聚合法、塊狀聚合法等。 An acrylic resin having a hydroxyl group as a base resin can be obtained by polymerizing a monomer component containing a (meth)acrylate having a hydroxyl group. The polymerization method can be appropriately selected from known polymerization methods such as various radical polymerizations, and examples thereof include suspension polymerization, solution polymerization, block polymerization, and the like.

於所述聚合方法中使單體成分聚合的情況下，亦可視需要而使用聚合起始劑。作為此種聚合起始劑，例如可列舉：過氧化酮、過氧化縮酮、過氧化氫、二烷基過氧化物、二醯基過氧化物、過氧化碳酸酯、過氧化酯、2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧基-2'-二甲基戊腈)等。 When the monomer component is polymerized in the polymerization method, a polymerization initiator may be used if necessary. Examples of such polymerization initiators include: peroxyketone, peroxyketal, hydrogen peroxide, dialkyl peroxide, dicarboxyl peroxide, peroxycarbonate, peroxyester, 2, 2'-Azobisisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(4-methoxy-2'-dimethyl valeronitrile) etc.

具有黏著劑層20的黏著片前驅物100可使用公知的方法進行製造。黏著片前驅物100例如可藉由以下製造方法而獲得，所述製造方法包括：利用分散介質來稀釋黏著劑層用的材料，製 備清漆的步驟；將所得的清漆塗敷於所述基材10上的步驟；以及自所塗敷的清漆中去除分散介質的步驟。 The adhesive sheet precursor 100 having the adhesive layer 20 can be manufactured using a known method. The adhesive sheet precursor 100 can be obtained, for example, by the following manufacturing method. The manufacturing method includes: diluting the material for the adhesive layer with a dispersion medium, and manufacturing The steps of preparing the varnish; applying the obtained varnish on the substrate 10; and removing the dispersion medium from the applied varnish.

黏著片前驅物100中的黏著劑層20的厚度可為0.1μm~30μm。若黏著劑層20的厚度為0.1μm以上，則有可確保充分的黏著力的傾向。若黏著劑層20的厚度為30μm以下，則有經濟上有利的傾向。 The thickness of the adhesive layer 20 in the adhesive sheet precursor 100 may be 0.1 μm~30 μm. When the thickness of the adhesive layer 20 is 0.1 μm or more, sufficient adhesive force tends to be ensured. If the thickness of the adhesive layer 20 is 30 μm or less, it tends to be economically advantageous.

黏著片前驅物100整體的厚度(基材10及黏著劑層20的合計厚度)可為5μm~150μm、50μm~150μm或100μm~150μm。 The overall thickness of the adhesive sheet precursor 100 (total thickness of the base material 10 and the adhesive layer 20) may be 5 μm to 150 μm, 50 μm to 150 μm, or 100 μm to 150 μm.

黏著片前驅物100可於實施電漿處理之前，於黏著劑層20的與基材10相反一側的面上貼附有保護材。保護材可使用與後述的保護材30中所例示者相同的保護材。 The adhesive sheet precursor 100 may have a protective material attached to the surface of the adhesive layer 20 opposite to the substrate 10 before plasma treatment. As the protective material, the same protective material as illustrated in the protective material 30 described below can be used.

<電漿處理的實施步驟> <Implementation steps of plasma treatment>

於本步驟中，對黏著片前驅物100中的黏著劑層20的與基材10相反一側的面實施電漿處理(圖1(b)的A)(參照圖1(b))。藉此，可製造具有已實施電漿處理A的黏著劑層(電漿處理後的黏著劑層20A)的黏著片110(參照圖1(c))。 In this step, plasma treatment is performed on the surface of the adhesive layer 20 in the adhesive sheet precursor 100 opposite to the base material 10 (A in FIG. 1(b) (refer to FIG. 1(b)). Thereby, the adhesive sheet 110 having the adhesive layer that has been subjected to the plasma treatment A (the adhesive layer 20A after the plasma treatment) can be manufactured (see FIG. 1( c )).

電漿為構成氣體的分子部分地或完全地電離，分成陽離子及電子而自由地運動的狀態。藉由使用電漿狀態的氣體來對黏著劑層的與基材相反一側的面進行處理，而於黏著劑層的表面進行化學反應，賦予含氧的親水性基，被處理面的接觸角降低，可提高潤濕性。利用該反應，能夠提高黏著片前驅物的黏著劑層20 的黏著力。 Plasma is a state in which the molecules constituting the gas are partially or completely ionized, separated into cations and electrons, and move freely. By using plasma-state gas to treat the surface of the adhesive layer on the opposite side to the substrate, a chemical reaction occurs on the surface of the adhesive layer to impart oxygen-containing hydrophilic groups, and the contact angle of the treated surface is Decreasing can improve wettability. Utilizing this reaction, the adhesive layer 20 of the adhesive sheet precursor can be improved. of adhesion.

電漿處理並無特別限制，就成本、處理能力、及減少損傷的觀點而言，可為使用大氣壓電漿的電漿處理。使用大氣壓電漿的電漿處理例如可使用超高密度大氣壓電漿單元(富士機械製造股份有限公司製造，商品名：FPB-20型號II(TYPE II))來實施。 The plasma treatment is not particularly limited, but from the viewpoint of cost, processing capability, and damage reduction, plasma treatment using atmospheric pressure plasma may be used. Plasma treatment using atmospheric pressure plasma can be performed, for example, using an ultra-high-density atmospheric pressure plasma unit (manufactured by Fuji Machinery Manufacturing Co., Ltd., trade name: FPB-20 Type II (TYPE II)).

關於電漿處理的處理溫度，就避免因電漿處理而對基材10及黏著劑層20造成損傷的觀點而言，較佳為以低於基材10的熔點或黏著劑層20的熔點中任一較低者的溫度來進行。電漿處理較佳為以在進行處理的時間內黏著片前驅物100(基材10及黏著劑層20)不產生褶皺、撓曲等的方式，即，黏著片不顯著地發生熱變形的方式，一邊調整處理溫度、處理速度等條件一邊進行。若產生褶皺、撓曲等，則有妨礙電漿處理時的裝置運轉之虞。電漿處理的溫度條件例如可為300℃以下、250℃以下、或200℃以下。 The treatment temperature of the plasma treatment is preferably lower than the melting point of the base material 10 or the melting point of the adhesive layer 20 from the viewpoint of avoiding damage to the base material 10 and the adhesive layer 20 due to the plasma treatment. whichever is the lower temperature. The plasma treatment is preferably performed in such a manner that the adhesive sheet precursor 100 (substrate 10 and adhesive layer 20 ) does not produce wrinkles, deflections, etc. during the treatment time, that is, the adhesive sheet does not significantly undergo thermal deformation. , while adjusting conditions such as processing temperature and processing speed. If wrinkles, deflections, etc. occur, the operation of the device during plasma processing may be hindered. The temperature condition of the plasma treatment may be, for example, 300°C or lower, 250°C or lower, or 200°C or lower.

電漿處理可調整處理面積。因此，可對黏著片前驅物100中的黏著劑層20的與基材10相反一側的面的一部分或全部實施電漿處理。若對黏著劑層20的面的一部分實施電漿處理，則由於可調整被處理面的接觸角，而可於同一面，容易地分開形成接觸角低的部分(即，黏著劑層的黏著力高的部分)及接觸角高的部分(即，黏著劑層的黏著力低的部分)。 Plasma treatment can adjust the treatment area. Therefore, plasma treatment may be performed on part or all of the surface of the adhesive layer 20 on the opposite side to the base material 10 in the adhesive sheet precursor 100 . If a part of the surface of the adhesive layer 20 is subjected to plasma treatment, the contact angle of the treated surface can be adjusted, and a portion with a low contact angle (that is, the adhesive force of the adhesive layer) can be easily separated on the same surface. The part with high contact angle) and the part with high contact angle (that is, the part with low adhesion of the adhesive layer).

<保護材的配置步驟> <Configuration steps of protective materials>

本步驟中，於已實施電漿處理的黏著劑層(電漿處理後的黏著劑層20A)的與基材10相反一側的面上貼附保護材30(參照圖1(d))。藉此，可獲得帶保護材的黏著片120。貼附保護材30的方法可使用公知的方法來進行貼附。 In this step, the protective material 30 is attached to the surface opposite to the base material 10 of the plasma-treated adhesive layer (the plasma-treated adhesive layer 20A) (see FIG. 1(d) ). Thereby, the adhesive sheet 120 with a protective material can be obtained. The protective material 30 can be attached using a known method.

保護材30並無特別限制，可使用在黏著劑的領域中所使用的保護膜。作為保護膜，例如可列舉：聚對苯二甲酸乙二酯膜等聚酯系膜；聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚乙酸乙烯酯膜等聚烯烴系膜；聚氯乙烯膜、聚醯亞胺膜等塑膠膜等。另外，保護膜可使用紙、不織布、金屬箔等。保護材30的電漿處理後的黏著劑層20A側的面，亦可藉由矽酮系剝離劑、氟系剝離劑、長鏈烷基丙烯酸酯系剝離劑等脫模劑來進行處理。 The protective material 30 is not particularly limited, and a protective film used in the field of adhesives can be used. Examples of the protective film include polyester films such as polyethylene terephthalate films; polytetrafluoroethylene films, polyethylene films, polypropylene films, polymethylpentene films, polyvinyl acetate films, etc. Polyolefin film; polyvinyl chloride film, polyimide film and other plastic films, etc. In addition, paper, non-woven fabric, metal foil, etc. can be used as the protective film. The surface of the protective material 30 on the adhesive layer 20A side after plasma treatment can also be treated with a release agent such as a silicone release agent, a fluorine release agent, or a long-chain alkyl acrylate release agent.

保護材30可為保護材30的貼附於電漿處理後的黏著劑層20A一側的面藉由電漿處理進行了處理者。藉由使用利用電漿處理進行了處理者作為保護材30，而有可長期維持電漿處理後的黏著劑層20A的潤濕性提高的狀態的傾向。 The protective material 30 may be one in which the surface of the protective material 30 attached to the adhesive layer 20A after plasma treatment has been treated by plasma treatment. By using one that has been treated by plasma treatment as the protective material 30 , the wettability of the adhesive layer 20A after the plasma treatment tends to be maintained in a state in which it is improved for a long period of time.

保護材30的厚度並無特別限制，可為5μm~500μm、10μm~200μm或15μm~100μm。 The thickness of the protective material 30 is not particularly limited, and can be 5 μm ~ 500 μm, 10 μm ~ 200 μm, or 15 μm ~ 100 μm.

[切晶-黏晶一體型帶的製造方法] [Manufacturing method of crystal cutting-crystal bonding integrated belt]

圖2(a)~圖2(c)是示意性地表示切晶-黏晶一體型帶的製造方法的一實施形態的剖面圖。本實施形態的切晶-黏晶一體型帶130的製造方法包括：對於藉由所述製造方法而獲得的黏著片 110，於電漿處理後的黏著劑層20A的與基材10相反一側的面(已實施電漿處理的面)上形成接著劑層40的步驟(參照圖2(a)、圖2(b))。 2(a) to 2(c) are cross-sectional views schematically showing an embodiment of a method for manufacturing a die-cutting-die-bonding integrated belt. The manufacturing method of the die cutting-die bonding integrated belt 130 of this embodiment includes: 110. The step of forming the adhesive layer 40 on the surface opposite to the base material 10 (the surface that has been plasma treated) of the plasma-treated adhesive layer 20A (refer to Figure 2(a), Figure 2( b)).

接著劑層40是包含接著劑成分的層。作為構成接著劑層40的接著劑成分，例如可列舉：熱硬化性接著劑成分、光硬化性接著劑成分、熱塑性接著劑成分、氧反應性接著劑成分等。就接著性的觀點而言，接著劑層較佳為包含熱硬化性接著劑成分。 The adhesive layer 40 is a layer containing an adhesive component. Examples of the adhesive components constituting the adhesive layer 40 include thermosetting adhesive components, photocurable adhesive components, thermoplastic adhesive components, oxygen-reactive adhesive components, and the like. From the viewpoint of adhesiveness, the adhesive layer preferably contains a thermosetting adhesive component.

就接著性的觀點而言，熱硬化性接著劑成分較佳為包含環氧樹脂及可成為環氧樹脂的硬化劑的酚樹脂。 From the viewpoint of adhesiveness, the thermosetting adhesive component preferably contains an epoxy resin and a phenol resin that serves as a hardener for the epoxy resin.

環氧樹脂只要為分子內具有環氧基者，則可並無特別限制地使用。作為環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、含二環戊二烯骨架的環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架的環氧樹脂、含茀骨架的環氧樹脂、三苯酚甲烷型環氧樹脂、聯苯型環氧樹脂、伸二甲苯基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、多官能酚類、蒽等多環芳香族類的二縮水甘油醚化合物等。該些可單獨使用一種或將兩種以上組合使用。以接著劑層總量為基準，環氧樹脂的含量可為2質量%~50質量%。 The epoxy resin can be used without particular restriction as long as it has an epoxy group in the molecule. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, stilbene-type epoxy resin, triazine skeleton-containing epoxy resin, Epoxy resins with fusun skeleton, trisphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, multifunctional phenols , anthracene and other polycyclic aromatic diglycidyl ether compounds. These can be used individually by 1 type or in combination of 2 or more types. Based on the total amount of the adhesive layer, the content of epoxy resin can be 2 to 50 mass%.

酚樹脂只要為分子內具有酚性羥基者，則可並無特別限制地使用。作為酚樹脂，例如可列舉：苯酚、甲酚、間苯二酚、 鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類與甲醛等具有醛基的化合物，於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂；由烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化萘二醇、苯酚酚醛清漆、苯酚等酚類及/或萘酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等。該些可單獨使用一種或將兩種以上組合使用。以接著劑層總量為基準，酚樹脂的含量可為2質量%~50質量%。 The phenol resin can be used without particular limitation as long as it has a phenolic hydroxyl group in the molecule. Examples of the phenol resin include: phenol, cresol, resorcinol, Phenols such as catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and/or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene, and formaldehyde and other aldehyde groups. Compound, novolac-type phenol resin obtained by condensation or co-condensation under acidic catalyst; composed of allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolak, phenol Phenol aralkyl resin, naphthol aralkyl resin, etc. synthesized from phenols and/or naphthols and dimethoxy-p-xylene or bis(methoxymethyl)biphenyl. These can be used individually by 1 type or in combination of 2 or more types. Based on the total amount of the adhesive layer, the content of the phenolic resin can be 2 to 50 mass%.

作為其他成分，接著劑層40亦可包含：三級胺、咪唑類、四級銨鹽類等硬化促進劑；氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、結晶質二氧化矽、非晶質二氧化矽等無機填料等。以接著劑層總量為基準，其他成分的含量可為0質量%~20質量%。 As other components, the adhesive layer 40 may also include: hardening accelerators such as tertiary amines, imidazoles, and quaternary ammonium salts; aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, and magnesium silicate. , calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, crystalline silica, amorphous silica and other inorganic fillers. Based on the total amount of the adhesive layer, the content of other components can be 0 mass% to 20 mass%.

於黏著片110中，對黏著劑層20的與基材10相反一側的面的一部分或全部實施電漿處理。於對黏著劑層20的與基材10相反一側的面的一部分實施電漿處理的情況下，接著劑層40可以覆蓋黏著劑層20的已實施電漿處理的面的一部分或全部的方式形成，亦可以覆蓋黏著劑層20的未實施電漿處理的面的一部分或全部的方式形成。另外，接著劑層40亦可以覆蓋黏著劑層20的已實施電漿處理的面及黏著劑層20的未實施電漿處理的面兩方的面的一部分或全部的方式形成。於對黏著劑層20的全部實施電漿處 理的情況下，接著劑層40可以覆蓋黏著劑層20的已實施電漿處理的面的一部分或全部的方式形成。 In the adhesive sheet 110 , a plasma treatment is performed on part or all of the surface of the adhesive layer 20 opposite to the base material 10 . When a part of the surface of the adhesive layer 20 opposite to the base material 10 is subjected to plasma treatment, the adhesive layer 40 may cover part or all of the surface of the adhesive layer 20 that has been subjected to the plasma treatment. It may be formed to cover part or all of the surface of the adhesive layer 20 that is not subjected to plasma treatment. In addition, the adhesive layer 40 may be formed so as to cover part or all of both the surface of the adhesive layer 20 that has been subjected to plasma treatment and the surface of the adhesive layer 20 that has not been subjected to plasma treatment. When applying plasma to the entire adhesive layer 20 If necessary, the adhesive layer 40 may be formed so as to cover part or all of the surface of the adhesive layer 20 that has been subjected to plasma treatment.

作為於電漿處理後的黏著劑層20A的與基材10相反一側的面上形成接著劑層40的方法，例如可列舉：使用公知的方法，將接著劑成分成形為膜狀，將所得的膜狀接著劑貼合於電漿處理後的黏著劑層20A的與基材10相反一側的面的方法。如上所述，可獲得切晶-黏晶一體型帶130(參照圖2(b))。 As a method of forming the adhesive layer 40 on the surface opposite to the base material 10 of the adhesive layer 20A after plasma treatment, for example, the adhesive component is formed into a film shape using a known method, and the resultant A method in which a film-like adhesive is bonded to the surface opposite to the base material 10 of the plasma-treated adhesive layer 20A. As described above, the die cutting-die bonding integrated belt 130 can be obtained (see FIG. 2(b) ).

切晶-黏晶一體型帶130可於接著劑層40的與黏著劑層20A相反一側的面上具備保護材50。保護材50並無特別限制，可使用切晶-黏晶一體型帶中所使用的保護膜。作為保護膜，例如可列舉：聚對苯二甲酸乙二酯膜等聚酯系膜；聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚乙酸乙烯酯膜等聚烯烴系膜；聚氯乙烯膜、聚醯亞胺膜等塑膠膜等。如上所述，可獲得帶保護材的切晶-黏晶一體型帶140(參照圖2(c))。 The die cutting-die bonding integrated belt 130 may be provided with a protective material 50 on the surface of the adhesive layer 40 opposite to the adhesive layer 20A. The protective material 50 is not particularly limited, and a protective film used in a die-bonding integrated tape can be used. Examples of the protective film include polyester films such as polyethylene terephthalate films; polytetrafluoroethylene films, polyethylene films, polypropylene films, polymethylpentene films, polyvinyl acetate films, etc. Polyolefin film; polyvinyl chloride film, polyimide film and other plastic films, etc. As described above, the die-bonding integrated tape 140 with the protective material can be obtained (see FIG. 2(c) ).

[半導體裝置(半導體封裝體)的製造方法] [Method for manufacturing semiconductor device (semiconductor package)]

圖3(a)~圖3(f)是示意性表示半導體裝置的製造方法的一實施形態的剖面圖。本實施形態的半導體裝置的製造方法包括：將藉由所述製造方法而獲得的切晶-黏晶一體型帶130的接著劑層40貼附於半導體晶圓W的步驟(晶圓層壓步驟，參照圖3(a)、圖3(b))；將半導體晶圓W、接著劑層40及已實施電漿處理的黏著劑層(電漿處理後的黏著劑層20A)單片化的步驟(切晶步驟，參照圖3(c))；視需要對已實施電漿處理的黏著劑層(電 漿處理後的黏著劑層20A)(經由基材10)照射紫外線的步驟(紫外線照射步驟，參照圖3(d))；自已實施電漿處理的黏著劑層(黏著劑層20Aa)拾取附著有接著劑層40a的半導體元件Wa(帶接著劑層的半導體元件60)的步驟(拾取步驟，參照圖3(e))；以及經由接著劑層40a，將帶接著劑層的半導體元件60接著於半導體元件搭載用支撐基板80的步驟(半導體元件接著步驟，參照圖3(f))。 3(a) to 3(f) are cross-sectional views schematically showing an embodiment of a method of manufacturing a semiconductor device. The manufacturing method of the semiconductor device of this embodiment includes the step of attaching the adhesive layer 40 of the die-cutting-die integrated tape 130 obtained by the manufacturing method to the semiconductor wafer W (wafer lamination step). , refer to Figure 3 (a), Figure 3 (b)); the semiconductor wafer W, the adhesive layer 40 and the adhesive layer that has been subjected to plasma treatment (the adhesive layer 20A after plasma treatment) are single-chip step (crystal cutting step, refer to Figure 3(c)); if necessary, the adhesive layer that has been subjected to plasma treatment (electrode The step of irradiating ultraviolet rays (ultraviolet irradiation step, see Figure 3(d)) to the adhesive layer 20A) after plasma treatment (via the base material 10); picking up the adhesive layer (adhesive layer 20Aa) that has been subjected to plasma treatment The step of attaching the semiconductor element Wa (semiconductor element 60 with the adhesive layer) to the adhesive layer 40a (pickup step, see FIG. 3(e)); and attaching the semiconductor element 60 with the adhesive layer to the adhesive layer 40a via the adhesive layer 40a. The step of mounting the semiconductor element mounting support substrate 80 (semiconductor element attaching step, see FIG. 3(f) ).

<晶圓層壓步驟> <Wafer lamination step>

首先，將切晶-黏晶一體型帶130配置於規定的裝置。繼而，於半導體晶圓W的主面Ws，經由接著劑層40而貼附切晶-黏晶一體型帶130(參照圖3(a)、圖3(b))。半導體晶圓W的電路面較佳為設置於與主面Ws為相反側的面。 First, the die-cutting-die-bonding integrated belt 130 is placed in a predetermined device. Next, the die-cutting-die-bonding integrated tape 130 is attached to the main surface Ws of the semiconductor wafer W via the adhesive layer 40 (see FIGS. 3(a) and 3(b) ). The circuit surface of the semiconductor wafer W is preferably provided on the surface opposite to the main surface Ws.

<切晶步驟> <Crystal cutting step>

其次，對半導體晶圓W、接著劑層40及電漿處理後的黏著劑層20A進行切晶(參照圖3(c))。此時，亦可將基材10的一部分切晶。如此，切晶-黏晶一體型帶130亦作為切晶片發揮功能。 Next, the semiconductor wafer W, the adhesive layer 40 and the plasma-treated adhesive layer 20A are diced (see FIG. 3(c) ). At this time, a part of the base material 10 may also be cut. In this way, the die-bonding integrated belt 130 also functions as a die-cutting chip.

<紫外線照射步驟> <Ultraviolet irradiation step>

對於電漿處理後的黏著劑層20A，可視需要(經由基材10)照射紫外線(參照圖3(d))。於黏著劑成分中的基體樹脂為藉由紫外線而硬化者(紫外線硬化型基體樹脂)的情況下，該黏著劑層20A硬化，可降低黏著劑層20A與接著劑層40之間的接著力。於紫外線照射中，較佳為使用波長200nm~400nm的紫外線。紫 外線照射條件較佳為將照度及照射量分別調整為30mW/cm2~240mW/cm2的範圍及200mJ/cm2~500mJ/cm2的範圍。 The plasma-treated adhesive layer 20A may be irradiated with ultraviolet rays (via the base material 10 ) if necessary (see FIG. 3(d) ). When the base resin in the adhesive component is one that is hardened by ultraviolet rays (ultraviolet curable base resin), the adhesive layer 20A hardens, which can reduce the bonding force between the adhesive layer 20A and the adhesive layer 40 . In ultraviolet irradiation, it is preferable to use ultraviolet rays with a wavelength of 200nm~400nm. Preferable ultraviolet irradiation conditions are to adjust the illumination intensity and irradiation amount to the range of 30mW/cm 2 ~240mW/cm 2 and the range of 200mJ/cm 2 ~500mJ/cm 2 respectively.

<拾取步驟> <Pickup steps>

其次，藉由將基材10擴張而使經切晶的帶接著劑層的半導體元件60彼此分開，並且利用抽吸夾頭74抽吸自基材10側由頂針72頂起的帶接著層的半導體元件60，且自黏著劑層20Aa進行拾取(參照圖3(e))。於對黏著劑層20的與基材10相反一側的面的一部分實施電漿處理的情況下，黏著劑層20Aa的接著劑層40a側的面可為經實施電漿處理的面，亦可為未實施電漿處理的面，亦可為包括經實施電漿處理的面及未實施電漿處理的面兩方的面。再者，帶接著劑層的半導體元件60具有半導體元件Wa及接著劑層40a。半導體元件Wa為半導體晶圓W藉由切晶而分割出者，接著劑層40a為接著劑層40藉由切晶而分割出者。黏著劑層20Aa為電漿處理後的黏著劑層20A藉由切晶而分割出者。當拾取帶接著劑層的半導體元件60時，黏著劑層20Aa可殘留在基材10上。於拾取步驟中，未必需要將基材10擴張，但藉由將基材10擴張，可進一步提高拾取性。 Next, the cut semiconductor elements 60 with the adhesive layer are separated from each other by expanding the base material 10 , and the suction chuck 74 is used to suck the adhesive layer-attached semiconductor elements lifted from the side of the base material 10 by the ejection pin 72 The semiconductor element 60 is picked up from the adhesive layer 20Aa (see FIG. 3(e) ). When a part of the surface of the adhesive layer 20 opposite to the base material 10 is subjected to plasma treatment, the surface of the adhesive layer 20Aa on the adhesive layer 40a side may be the surface that has been subjected to plasma treatment, or it may be It is a surface that has not been subjected to plasma treatment, and may include both a surface that has been subjected to plasma treatment and a surface that has not been subjected to plasma treatment. Furthermore, the semiconductor element 60 with an adhesive layer has a semiconductor element Wa and an adhesive layer 40a. The semiconductor element Wa is obtained by dividing the semiconductor wafer W by dicing, and the adhesive layer 40 a is obtained by dividing the adhesive layer 40 by dicing. The adhesive layer 20Aa is obtained by cutting the adhesive layer 20A after plasma treatment and dividing it. When the semiconductor device 60 with the adhesive layer is picked up, the adhesive layer 20Aa may remain on the substrate 10 . In the pick-up step, it is not necessarily necessary to expand the base material 10, but by expanding the base material 10, the pick-up performance can be further improved.

由頂針72產生的頂起量可適當設定。進而，就確保對極薄晶圓亦充分的拾取性的觀點而言，例如亦可進行兩段或三段的頂起。另外，亦可藉由使用抽吸夾頭74的方法以外的方法來拾取帶接著劑層的半導體元件60。 The amount of lifting produced by the ejector pin 72 can be appropriately set. Furthermore, from the viewpoint of ensuring sufficient pick-up properties even for extremely thin wafers, for example, two-stage or three-stage lifting may be performed. In addition, the semiconductor element 60 with the adhesive layer can also be picked up by a method other than the method using the suction chuck 74 .

<半導體元件接著步驟> <Semiconductor element attachment steps>

於拾取帶接著劑層的半導體元件60後，藉由熱壓接並經由接著劑層40a將帶接著劑層的半導體元件60接著於半導體元件搭載用支撐基板80(參照圖3(f))。半導體元件搭載用支撐基板80上可接著多個帶接著劑層的半導體元件60。 After picking up the semiconductor element 60 with the adhesive layer, the semiconductor element 60 with the adhesive layer is bonded to the semiconductor element mounting support substrate 80 through the adhesive layer 40 a by thermocompression bonding (see FIG. 3( f )). A plurality of semiconductor elements 60 with adhesive layers can be bonded to the semiconductor element mounting support substrate 80 .

本實施形態的半導體裝置的製造方法視需要可進而包括：藉由打線接合線70而將半導體元件Wa與半導體元件搭載用支撐基板80電性連接的步驟；以及於半導體元件搭載用支撐基板80的表面80a上，使用樹脂密封材92對半導體元件Wa進行樹脂密封的步驟。 The manufacturing method of the semiconductor device of this embodiment may further include, if necessary, the steps of electrically connecting the semiconductor element Wa and the semiconductor element mounting support substrate 80 through the wire bonding wire 70; On the surface 80a, the semiconductor element Wa is resin-sealed using a resin sealing material 92.

圖4是示意性表示半導體裝置的一實施形態的剖面圖。圖4所示的半導體裝置200可藉由經過所述步驟而製造。半導體裝置200亦可於半導體元件搭載用支撐基板80的與表面80a相反一側的面形成有焊球94，用於與外部基板(母板(mother board))的電性連接。 4 is a cross-sectional view schematically showing an embodiment of a semiconductor device. The semiconductor device 200 shown in FIG. 4 can be manufactured by going through the above steps. The semiconductor device 200 may have solder balls 94 formed on the surface of the semiconductor element mounting support substrate 80 opposite to the surface 80 a for electrical connection with an external substrate (mother board).

[黏著劑的處理方法] [How to handle adhesive]

一實施形態的黏著劑的處理方法包括：對黏著劑實施電漿處理的步驟。黏著劑可與所述黏著片的製造方法中所例示的黏著劑相同。電漿處理可與所述黏著片的製造方法中所例示的電漿處理相同。電漿處理可為使用大氣壓電漿的電漿處理。電漿處理的處理溫度可低於黏著劑的熔點。 An adhesive processing method according to one embodiment includes the step of subjecting the adhesive to plasma treatment. The adhesive agent may be the same as the adhesive agent illustrated in the manufacturing method of the adhesive sheet. The plasma treatment may be the same as that illustrated in the method for manufacturing the adhesive sheet. The plasma treatment may be plasma treatment using atmospheric pressure plasma. Plasma treatment can be performed at temperatures below the melting point of the adhesive.

[被黏著體的固定方法] [How to fix the adherend]

一實施形態的被黏著體的固定方法包括：經由藉由所述方法 進行了處理的黏著劑，將第二被黏著體貼附於第一被黏著體的步驟。作為第一被黏著體及第二被黏著體，並無特別限制，可列舉金屬被黏著體(不鏽鋼(SUS)、鋁等)、非金屬被黏著體(聚碳酸酯、玻璃等)等。被黏著體的固定條件可根據黏著劑的種類、以及第一被黏著體及第二被黏著體的種類而適當設定。 A method of fixing an adherend in one embodiment includes: by the method described above The processed adhesive is used to attach the second adherend to the first adherend. The first adherend and the second adherend are not particularly limited, and examples include metal adherends (stainless steel (SUS), aluminum, etc.), non-metal adherends (polycarbonate, glass, etc.), and the like. The fixing conditions of the adherend can be appropriately set according to the type of adhesive and the types of the first adherend and the second adherend.

[被黏著體的剝離方法] [Removal method of adherend]

一實施形態的被黏著體的剝離方法包括：利用水來對藉由所述方法進行了固定的被黏著體的第一被黏著體與黏著劑的界面或第二被黏著體與黏著劑的界面的至少一者進行處理(與水接觸)，將第一被黏著體及第二被黏著體剝離的步驟。相較於未實施電漿處理的黏著劑，已實施電漿處理的黏著劑的親水性基多，藉由利用水來進行處理(與水接觸)，而有容易剝離的傾向。再者，當剝離第一被黏著體及第二被黏著體時，黏著劑可附著於第一被黏著體或第二被黏著體的任一者上，亦可自第一被黏著體及第二被黏著體脫離。 A method for peeling off an adherend according to one embodiment includes using water to remove an interface between a first adherend and an adhesive or an interface between a second adherend and an adhesive of an adherend fixed by the method. A step of treating (contacting with water) at least one of the first and second adherends to peel off the first adherend and the second adherend. Compared with an adhesive that has not been subjected to plasma treatment, an adhesive that has been subjected to plasma treatment has more hydrophilic groups and is likely to be easily peeled off due to treatment with water (contact with water). Furthermore, when the first adherend and the second adherend are peeled off, the adhesive can adhere to either the first adherend or the second adherend, or can be removed from the first adherend and the second adherend. The second is detached from the adhesive body.

[實施例] [Example]

以下，基於實施例對本發明進行具體說明，但本發明並不限定於該些實施例。 Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples.

(實施例1) (Example 1)

[黏著片的製作] [Production of adhesive sheets]

<黏著片前驅物的準備> <Preparation of adhesive sheet precursor>

依據溶液聚合法，使作為單體的丙烯酸2-乙基己酯及甲基丙 烯酸甲酯、以及作為含官能基的單體的丙烯酸羥基乙酯及丙烯酸聚合，藉此獲得具有羥基的丙烯酸系樹脂。具有羥基的丙烯酸系樹脂的重量平均分子量為40萬，玻璃轉移點為-38℃。 According to the solution polymerization method, 2-ethylhexyl acrylate and methylpropyl acrylate are used as monomers. Methyl acrylate, hydroxyethyl acrylate as a functional group-containing monomer, and acrylic acid are polymerized to obtain an acrylic resin having a hydroxyl group. The weight average molecular weight of the acrylic resin having a hydroxyl group is 400,000, and the glass transition point is -38°C.

重量平均分子量是使用東曹(Tosoh)股份有限公司製造的SD-8022/DP-8020/RI-8020作為凝膠滲透層析(gel permeation chromatography，GPC)裝置，使用日立化成股份有限公司製造的凝膠組件(Gel pack)GL-A150-S/GL-A160-S作為管柱，以及使用四氫呋喃作為溶離液來測定聚苯乙烯換算的重量平均分子量(Mw)。 The weight average molecular weight is determined by using SD-8022/DP-8020/RI-8020 manufactured by Tosoh Co., Ltd. as a gel permeation chromatography (GPC) device, and using a gel permeation chromatography (GPC) device manufactured by Hitachi Chemical Co., Ltd. Gel pack (Gel pack) GL-A150-S/GL-A160-S was used as the column and tetrahydrofuran was used as the eluent to measure the weight average molecular weight (Mw) in terms of polystyrene.

玻璃轉移點是藉由以下的關係式(FOX式)而算出。 The glass transition point is calculated from the following relational formula (FOX formula).

1/Tg=Σ(Xi/Tgi) 1/Tg=Σ(X i /Tg i )

[所述式中，Tg表示共聚物的玻璃轉移點(K)。Xi表示各單體的質量分率，X1+X2+...+Xi+...+Xn=1。Tgi表示各單體的均聚物的玻璃轉移點(K)] [In the formula, Tg represents the glass transition point (K) of the copolymer. X i represents the mass fraction of each monomer, X 1 +X 2 +...+X i +...+X n =1. Tg i represents the glass transition point (K) of the homopolymer of each monomer]

使用三合一馬達(three-one motor)及攪拌翼，相對於具有羥基的丙烯酸系樹脂100質量份而調配12質量份的多官能異氰酸酯交聯劑(三菱化學股份有限公司製造，商品名「麥太科(MITEC)NY730A-T」)，並進行攪拌，藉此獲得黏著劑層形成用清漆。 Using a three-one motor and a stirring blade, 12 parts by mass of a multifunctional isocyanate cross-linking agent (manufactured by Mitsubishi Chemical Co., Ltd., trade name MITEC NY730A-T") and stirred to obtain a varnish for forming an adhesive layer.

使用敷料器，將所得的黏著劑層形成用清漆，以黏著劑 層的厚度成為10μm的方式，一邊調整間隙一邊塗敷於基材膜A(厚度38μm的聚對苯二甲酸乙二酯膜)上。於使所塗敷的黏著劑層形成用清漆於80℃下乾燥5分鐘後，將表面已實施電暈處理的基材膜B(厚度80μm的聚烯烴系膜)層壓於黏著劑層上，並於室溫(25℃)下放置2週，充分地進行老化，藉此獲得具有基材膜A/黏著劑層/基材膜B的構成的黏著片前驅物。 Using an applicator, apply the resulting adhesive layer-forming varnish to the adhesive The layer was applied on the base film A (polyethylene terephthalate film with a thickness of 38 μm) while adjusting the gap so that the thickness of the layer became 10 μm. After the applied varnish for forming an adhesive layer was dried at 80° C. for 5 minutes, the base film B (polyolefin-based film with a thickness of 80 μm) whose surface was corona-treated was laminated on the adhesive layer. It was left at room temperature (25° C.) for 2 weeks to fully age, thereby obtaining an adhesive sheet precursor having the composition of base film A/adhesive layer/base film B.

<電漿處理的實施> <Implementation of Plasma Treatment>

剝去黏著片前驅物的基材膜A，使用超高密度大氣壓電漿單元(富士機械製造股份有限公司製造，商品名：FPB-20 TYPE II)，對黏著片前驅物中的黏著劑層的與基材膜B相反一側的面實施電漿處理，製作黏著片。其後，於已實施電漿處理的黏著劑層的面上，配置保護材(聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)膜)，獲得實施例1的帶保護材的黏著片。 The base film A of the adhesive sheet precursor was peeled off, and an ultra-high-density atmospheric pressure plasma unit (manufactured by Fuji Machinery Manufacturing Co., Ltd., trade name: FPB-20 TYPE II) was used to remove the adhesive layer in the adhesive sheet precursor. The surface opposite to the base film B is subjected to plasma treatment to produce an adhesive sheet. Thereafter, a protective material (polyethylene terephthalate (PET) film) was placed on the surface of the adhesive layer that had been subjected to plasma treatment to obtain the adhesive sheet with protective material of Example 1.

(電漿處理的條件) (Conditions for plasma treatment)

加熱器的使用：不使用 Heater usage: Not used

照射速度：500mm/秒 Irradiation speed: 500mm/second

照射距離：5mm Illumination distance: 5mm

狹縫噴嘴：20mm寬 Slit nozzle: 20mm wide

使用氣體：氮氣及空氣 Gas used: nitrogen and air

氣體流量：氮氣60L/分鐘、空氣21L/分鐘 Gas flow: nitrogen 60L/min, air 21L/min

重覆數：1次(照射方法：20mm寬×8線) Number of repetitions: 1 time (Irradiation method: 20mm wide × 8 lines)

樣品尺寸：150mm×150mm Sample size: 150mm×150mm

再者，調整照射距離、照射速度、加熱器設定等，且以處理溫度為100℃以下的方式進行設定，以使在進行處理的時間內黏著片前驅物100(基材10及黏著劑層20)不產生褶皺、撓曲等。 Furthermore, the irradiation distance, irradiation speed, heater setting, etc. are adjusted, and the processing temperature is set to be 100° C. or lower, so that the adhesive sheet precursor 100 (base material 10 and adhesive layer 20 ) does not produce wrinkles, deflections, etc.

(實施例2) (Example 2)

對保護材的黏著劑層側的面，實施與對黏著劑層所實施的電漿處理相同的電漿處理(重覆數：1次)，除此以外，以與實施例1相同的方式進行，獲得實施例2的帶保護材的黏著片。 The same procedure as in Example 1 was performed except that the surface of the protective material on the adhesive layer side was subjected to the same plasma treatment as that performed on the adhesive layer (number of repetitions: 1 time). , the adhesive sheet with protective material of Example 2 was obtained.

(實施例3) (Example 3)

將保護材的電漿處理的重覆數自1次變更為4次，除此以外，以與實施例2相同的方式進行，獲得實施例3的帶保護材的黏著片。 Except for changing the number of repetitions of plasma treatment of the protective material from 1 to 4 times, the same procedure as in Example 2 was performed to obtain the adhesive sheet with protective material of Example 3.

(實施例4) (Example 4)

將黏著劑層的電漿處理的重覆數自1次變更為4次，除此以外，以與實施例1相同的方式進行，獲得實施例2的帶保護材的黏著片。 Except for changing the number of repetitions of plasma treatment of the adhesive layer from 1 to 4 times, the same procedure as in Example 1 was performed to obtain the adhesive sheet with protective material of Example 2.

(實施例5) (Example 5)

對保護材的黏著劑層側的面，實施與對黏著劑層所實施的電漿處理相同的電漿處理(重覆數：1次)，除此以外，以與實施例4相同的方式進行，獲得實施例5的帶保護材的黏著片。 The same procedure as in Example 4 was performed except that the surface of the protective material on the adhesive layer side was subjected to the same plasma treatment as that performed on the adhesive layer (number of repetitions: 1 time). , the adhesive sheet with protective material of Example 5 was obtained.

(實施例6) (Example 6)

將保護材的電漿處理的重覆數自1次變更為4次，除此以外，以與實施例5相同的方式進行，獲得實施例6的帶保護材的黏著 片。 Except for changing the number of repetitions of plasma treatment of the protective material from 1 to 4 times, the same procedure as in Example 5 was performed to obtain the adhesion with protective material of Example 6. piece.

(比較例1) (Comparative example 1)

未對黏著劑層實施電漿處理，除此以外，以與實施例1相同的方式進行，獲得比較例1的帶保護材的黏著片。 Except that the adhesive layer was not subjected to plasma treatment, the same procedure as in Example 1 was performed to obtain the adhesive sheet with protective material of Comparative Example 1.

[評價] [evaluation]

<水對黏著劑層的已實施電漿處理的面的接觸角的測定> <Measurement of the contact angle of water on the plasma-treated surface of the adhesive layer>

對於實施例1~實施例6及比較例1的帶保護材的黏著片，測定水對已實施電漿處理的面的接觸角。測定中，使用接觸角計(協和界面化學股份有限公司製造，商品名：卓普馬斯特(Drop Master)300)。藉由以下方式進行測定：將帶保護材的黏著片的保護材剝離，於黏著劑層的已實施電漿處理的面滴加水作為探針液體。測定條件是將溫度設為23℃~28℃，將探針液體的液滴量設為1.5μL，將測定時機設為探針的液滴下後5秒。將測定的試行數設為10次，求出所得的數值的中位數作為接觸角θ。將結果示於表1中。 For the protective-material-attached adhesive sheets of Examples 1 to 6 and Comparative Example 1, the contact angle of water on the plasma-treated surface was measured. In the measurement, a contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd., trade name: Drop Master 300) was used. The measurement is performed by peeling off the protective material of the adhesive sheet with the protective material, and adding water as a probe liquid dropwise to the plasma-treated surface of the adhesive layer. The measurement conditions were as follows: the temperature was set to 23°C to 28°C, the droplet amount of the probe liquid was set to 1.5 μL, and the measurement timing was set to 5 seconds after the droplet of the probe liquid was dropped. The number of trial measurements was set to 10, and the median of the obtained values was determined as the contact angle θ. The results are shown in Table 1.

Figure 108119835-A0305-02-0023-1
Figure 108119835-A0305-02-0023-1

<黏著劑層對SUS基板的剝離強度的測定> <Measurement of peel strength of adhesive layer to SUS substrate>

將實施例1、實施例2及比較例1的帶保護材的黏著片切成寬度10mm、長度70mm以上，且將保護材自帶保護材的黏著片剝離後貼附於SUS板(SUS430BA)，將其作為初期的測定樣品。貼附於SUS板時，利用3kg的錘輥在樣品上往返3次。將剝離引導帶(王子塔克(OJITAC)公司製造，EC帶)切成寬度10mm，於樣品的前端黏貼10mm左右，固定於荷重元(load cell)的前端。以剝離的進展與帶寬度平行的方式對荷重元的位置進行微調。另外，將初期的測定樣品冷藏(5℃)保管3個月，將其作為經過3個月的測定樣品。對於該些測定樣品，以剝離角度30度、剝離速度50mm/分鐘進行SUS基板與黏著劑層的剝離，求出剝離強度。另外，SUS基板是在使用前利用丙酮清洗後使用。將結果示於表2中。另外，表2中的數值是將比較例1的剝離強度的數值作為基準的相對值。 The adhesive sheet with protective material of Example 1, Example 2 and Comparative Example 1 was cut into a width of 10 mm and a length of 70 mm or more, and the protective material was peeled off from the adhesive sheet with protective material and then attached to the SUS board (SUS430BA). This was used as an initial measurement sample. When attaching to the SUS board, use a 3kg hammer roller to move back and forth on the sample 3 times. Cut the peeling guide tape (EC tape manufactured by OJITAC Co., Ltd.) to a width of 10 mm, stick it to the front end of the sample for about 10 mm, and fix it to the front end of the load cell. The position of the load cell is fine-tuned in such a way that the progression of peeling is parallel to the belt width. In addition, the initial measurement sample was stored in a refrigerator (5° C.) for 3 months, and was used as a 3-month-old measurement sample. For these measurement samples, the SUS substrate and the adhesive layer were peeled off at a peeling angle of 30 degrees and a peeling speed of 50 mm/minute, and the peeling strength was determined. In addition, the SUS substrate is cleaned with acetone before use. The results are shown in Table 2. In addition, the numerical values in Table 2 are relative values based on the numerical value of the peel strength of Comparative Example 1.

Figure 108119835-A0305-02-0024-2
Figure 108119835-A0305-02-0024-2

可推測，於使用例如以其他丙烯酸系樹脂、合成橡膠、天然橡膠、聚醯亞胺樹脂等為基體樹脂者來代替實施例1~實施例6的帶保護材的黏著片中的黏著劑層的情況下，亦可獲得同樣的效 果。 It can be speculated that when using other acrylic resins, synthetic rubbers, natural rubbers, polyimide resins, etc. as base resins instead of the adhesive layers in the adhesive sheets with protective materials of Examples 1 to 6, In this case, the same effect can be obtained fruit.

與比較例1的帶保護材的黏著片相比，實施例1~實施例6的帶保護材的黏著片中，黏著劑層的已實施電漿處理的面的接觸角降低，黏著劑層的潤濕性提高。另外，與比較例1的帶保護材的黏著片相比，實施例1、實施例2的帶保護材的黏著片的剝離強度提高，黏著力提高。另外，由實施例1與實施例2的對比而判明，藉由亦對保護材實施電漿處理，可長期維持實施了電漿處理的效果。由該些結果可確認到，本發明的製造方法能夠製造黏著力優異的黏著片。 Compared with the adhesive sheet with a protective material in Comparative Example 1, in the adhesive sheets with a protective material in Examples 1 to 6, the contact angle of the plasma-treated surface of the adhesive layer is reduced, and the contact angle of the adhesive layer is Improved wettability. In addition, compared with the adhesive sheet with protective material of Comparative Example 1, the peel strength of the adhesive sheet with protective material of Examples 1 and 2 was improved, and the adhesive force was improved. In addition, from the comparison between Example 1 and Example 2, it was found that by also performing plasma treatment on the protective material, the effect of the plasma treatment can be maintained for a long period of time. From these results, it was confirmed that the manufacturing method of the present invention can produce an adhesive sheet with excellent adhesive force.

10:基材 10:Substrate

20:黏著劑層 20: Adhesive layer

20A:電漿處理後的黏著劑層 20A: Adhesive layer after plasma treatment

30:保護材 30:Protective material

100:黏著片前驅物 100:Adhesive sheet precursor

110:黏著片 110: Adhesive sheet

120:帶保護材的黏著片 120: Adhesive sheet with protective material

A:電漿處理 A: Plasma treatment

Claims (3)

一種黏著片的製造方法，包括：準備黏著片前驅物的步驟，所述黏著片前驅物具有基材、及設置於所述基材上的黏著劑層；對所述黏著片前驅物中之所述黏著劑層的與所述基材相反側的面實施電漿處理的步驟；以及於已實施電漿處理的所述黏著劑層的與所述基材相反側的面上貼附保護材的步驟，其中所述保護材的貼附於已實施電漿處理的所述黏著劑層的一側的面藉由電漿處理進行了處理。 A method for manufacturing an adhesive sheet, including the steps of preparing an adhesive sheet precursor having a base material and an adhesive layer disposed on the base material; The step of subjecting the surface of the adhesive layer opposite to the base material to plasma treatment; and attaching a protective material to the surface of the plasma-treated adhesive layer opposite to the base material. In the step, a surface of the protective material attached to the side of the adhesive layer that has been subjected to plasma treatment is treated by plasma treatment. 如申請專利範圍第1項所述的黏著片的製造方法，其中所述電漿處理為使用大氣壓電漿的電漿處理。 The method for manufacturing an adhesive sheet as described in Item 1 of the patent application, wherein the plasma treatment is a plasma treatment using atmospheric pressure plasma. 如申請專利範圍第1項或第2項所述的黏著片的製造方法，其中所述電漿處理的處理溫度小於所述基材的熔點或所述黏著劑層的熔點中任一較低者的溫度。 The manufacturing method of an adhesive sheet as described in item 1 or 2 of the patent application, wherein the processing temperature of the plasma treatment is lower than the melting point of the base material or the melting point of the adhesive layer, whichever is lower temperature.
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